Dr. Haoshen ZHOU ([email protected]) Group Leader of Energy Interface Technology Group Energy Technology Research Institute, AIST, Tsukuba, Japan A new type Li-Cu battery &Li-Air battery/fuel cell How to develop post lithium ion battery based on new concepts 1 To develop the HEV, PHEV, EV We face: Energy problem! Environmental problem! Oil problem! 2 The key technology of EV is battery technology The practice application always limited by the battery technology at that time. (From Webs of Wikipedia and Nissan) 1947 Tama Auto-motors’ EV A long history of EV, A dream of human being! 3 (From J.M.Tarascon, M.Armand, Nature, 414, 2001, 359 ) The history of rechargeable batteries 4 Li + Discharge Metal Oxide Positive Charge Discharge Carbon Negative charge Metal Oxide Positive ← e－ 400 (W/kg) Power Density 1200 (W/kg) 150-300 (Wh/kg) Plug in EV 800-1000 (Wh/kg)!! 1000 (W/kg) EV To increase both the energy and power densities ! 150 (Wh/kg) Energy Density Small EV & HEV According to NEDO’s suggestion! 7-8 time of now’s level What is the necessary energy & power densities for EV? Carbon Negative e－ → 5 60C AB: 12 wt% 1.5 2.0 2.5 3.0 3.5 4.0 4.5 0 b 20 60 80 /g Capacity ( mAh/g ) 40 2 A 100 1 A /g 120 5 0. /g 140 A A /g 160 1 0. AB: 0 wt% The challenge is how to improve the energy density Zhou et. al. Angew. Chem. Int. Ed. 47, (2008), 7461 a) 83 wt.% LiFePO4/C, 12 wt.% AB, 5 wt.% PTFE b) Without acetylene black(AB) a + The power density has been remarkable improved by nanostructure active material： Potential (V, vs. Li/Li ) 6 Li + Discharge Metal Oxide Positive Charge Discharge Rocking Chair Carbon Negative charge Metal Oxide Positive ← e－ The Concept of Rocking Chair should be broken to develop next generation battery with large energy density Anode active (mAh/g): LiC6(372), Li4.4Sn(994), Li4.4Si(4000), Li(3800) Cathode active (mAh/g): LiCoO2(130), LiMn2O4(120), LiFeO4(170), VOx(350)etc Carbon Negative e－ → Is it possible to increase the energy density of now’s LIB by 7 or 8 times? 7 Potential ( V, vs. Li/Li+ ) Capacity (mAh g-1) How to develop next generation battery? Negative Materials Positive Materials 8 (mAh/g) M : element active material • For strategy design: (a) z > 1.0 (b) use LiMx or M as active • C = zF / (weight of LiMxOy) • Generally the theoretical value of cathode active materials LiMxOy (here: M metal; O can be replace by F, S, PO4etc.) • The problem is improve the cathode active How to increase the cathode capacities? 9 • • • • • • • • • • • Li + e- Ù Li+ Na + e- Ù Na+ Mg + 2e- Ù Mg2+ Ca + 2e- Ù Ca2+ Mn + 2e- Ù Mn2+ Fe + 2e- Ù Fe2+ Co + 2e- Ù Co2+ Ni + 2e- Ù Ni2+ Cu + 2e- Ù Cu2+ Ag + e- Ù Ag+ Au + e- Ù Au+ Voltage= 3.4 V Beyond Lithium ion battery -3.045 Eo/V -2.714 Eo/V -2.356 Eo/V -2.84 Eo/V -1.18 Eo/V -0.44 Eo/V -0.277 Eo/V -0.257 Eo/V 0.34 Eo/V 0.799 Eo/V 1.84 Eo/V 10 Is it possible to design a new type Li-Cu Rechargeable Battery ? cathode active material Periodic Table of the Elements Anode active material 11 From Li ion battery into Li-Cu rechargeable battery with hybrid electrolytes 12 John Fredric Daniel For charging, Zn will be coated by Cu layer !! However, this is primary battery !! Anode: Zn → Zn2+ + 2eCathode： Cu2+ + 2e- → Cu Alessandro Volta • Use M (metal) as cathode active • Metal-metal battery • The first primary battery is Zn-Cu battery. Metal-Metal battery 13 Aqueous electrolyte for Cu Cu Organic-Aqueous Hybrid Electrolyte Liquid-Solid Hybrid Electrolyte Hybrid electrolytes LISICON: only Li+ can pass through LISICON Organic electrolyte for Li Li+ Li+ Cu2+ Developing Hybrid Electrolyte 14 Composition:Li2O-Al2O3-SiO2-P2O5-TiO2-GeO2 (Li1+x+yAlx(Ti,Ge)2-xSiyP3-yO12) Lithium ion conductivity （1×10-4S/cm at 25℃） (Provided by Ohara Company) 15 aqueous NO3- Li+ Cu2+ Cathode Cu Discharge: Cathode: Cu2+ + 2e- → Cu Anode: Li → Li+ + e- Charge： Cathode: Cu → Cu2+ + 2eAnode: Li+ + e- → Li Wang and Zhou, Electrochemistry Communications, 11, (2009), 1834 hybrid electrolytes LISICON Li+ ClO4- Organic electrolyte Anode Li - e- e- Discharge + Charge The structure of Lithium Cupper Rechargeable Battery 16 Li+ Non-aqueous Liquid solution V - Negative (Graphite) Positive + (Lix Host ) (a) Lithium ion battery e-1 e-1 V Li+ Li+ Non-aqueous Liquid solution Discharge e-1 - Negative (Graphite) (b) Lithium cupper rechargeable battery Beyond Lithium ion battery Positive + (Lix Host ) e-1 Charge Design rechargeable Li-Cu Battery with hybrid electrolytes 17 -0.0016 -0.0008 0.0000 0.0008 0.0016 0.0024 2.6 2.8 3.2 + 3.4 Potential (V, vs. Li/Li ) 3.0 3.6 Cu deposition Cu dissolution 3.8 Wang and Zhou, Electrochemistry Communications, 11, (2009), 1834 Current ( A ) 18 Potential ( V, vs. Li/Li ) + 0 1 2 3 4 5 0 b 2 2+ Cu 200 400 2+ Cu 600 -1 Capaciyt ( mAh g ) Cu 2 Discharge at 1 mA/cm Charge at 1 mA/cm for 16 h Cu 800 19 Potential ( V, vs. Li/Li ) 0 1 2 3 4 5 0 2 2 2 2 200 -1 600 Capaciyt ( mAh g ) 400 800 2+ Cu 3 mA/cm 2 mA/cm 1 mA/cm2 0.5 mA/cm2 Charge at 1 mA/cm for 16 h 2+ Cu Discharge at different currents Cu 4 mA/cm b Cu Wang and Zhou, Electrochemistry Communications, 11, (2009), 1834 + 20 Potential (V, vs. Li/Li ) + 0 1 2 3 4 5 6 0 20 30 2+ Cu 40 50 2+ Cu Charge-discharge cycle time (hours) 10 Cu Cu 60 21 Discharge capacity ( mAh g ) -1 0 b 20 60 Cycle number 40 80 100 0 20 40 60 80 100 120 140 160 Wang and Zhou, Electrochemistry Communications, 11, (2009), 1834 0 200 400 600 800 1000 1200 Coulombic efficiency ( % ) 22 23 High temperature Solid-state reaction [ Ishihara, K. 5th Int. Conf. Ecobalance, Tsukuba (2002).] 70 kg CO2 per kWh Extracting the raw materials Preparation of conventional cathode Why renewable battery is necessary ? 24 (http://www.iloveebikes.com/batteries.html) Recycling ? Recycling of conventional cathode is very difficult! 25 e- Li+ aqueous Li+ Cu2+ Discharge: Cathode: Cu2+ + 2e- → Cu Anode: Li → Li+ + e- Charge： Cathode: Cu → Cu2+ + 2eAnode: Li+ + e- → Li Wang and Zhou, Electrochemistry Communications, 11, (2009), 1834 Cathode Cu e- Discharge + LISICON Organic electrolyte Anode Li - Charge Li-Cu rechargeable battery is a renewable (or recyclable) battery 26 • To develop new type Li-Air Battery • The Li-Cu rechargeable battery can not satisfy 1000Wh/kg for EV. To develop New Type Li-Air Battery 27 Abraham K.M., et al, ; J. Electrochem. Soc. Vol.143, (1996),1 • Theoretically, the capacity of cathode (or air electrode) can be remarkable large because cathode active O2 is not included in battery package. For energy density: 1350Wh/kg • Zn-Air： 2Zn+O2=>2ZnO 4180Wh/kg • Ca-Air: 2Ca+O2=>2CaO 8130Wh/kg • Al-Air: 4Al+3O2=>2Al2O3 11140Wh/kg • Li-Air: 4Li+O2=>2Li2O Metal－Air Battery 28 Prof. P. G. Bruce, et al, ; J. Am. Chem. Soc. Vol.128, (2006), 1390 Cycle performance has been improved by Bruce’s group. Dr.Abraham K.M., et al, ; J. Electrochem. Soc. Vol.143, (1996),1 The 1st paper about Li-Air battery 29 Organic electrolyte V e-1 Porous electrode containing catalyst O2 Li+ Carbon Catalyst Lithium e-1 Organic electrolyte V e-1 Porous electrode containing catalyst O2 Lii 2O2 L Li+ Carbon Catalyst The discharge product Li2O2 or Li2O is not soluble in organic electrolyte, which inevitably clogs porous catalytic electrode. After fully clogged by formed Li2O2 deposit, the porous catalytic electrode cannot reduce O2 from environment any more. Lithium e-1 The problems of conventional Li-Air Battery 30 Wang and Zhou, Journal of Power Sources, 195, (2010), 358 (3) to use hybrid electrolyte: organic electrolyte for anode area, aqueous electrolyte for cathode area, and LISICON as a separator which only let Li ion pass through it. (2) O2 + 2H2O + 4e- → 4OH- (1) to release soluble discharge product as FC Design new type lithium Air Battery 31 LIB Anode Area Organic Electrolyte Anode Li Li+ FC FC Are正極側 Electrode Area Hybrid Electrolyte Hybrid of LIB and FC Separate Area LISICON Air Air Electrode Aqueous Catalyst （Porous Carbon） OH - Li+ OH - How to design the New Type Lithium Air Battery 32 OH - Li + OH - LISICON 空気 Air FC Air Electrode Area Air Electrode (carbon porous) + Organic electrolyteaqueous Catalyst Anode 金属 Li Li + + LISICON = OHARA Glass, 0.15 millimeter, 10-4 S cm-1 Li︱organic electrolyte︱LISICON｜10ml 1 M KOH｜Mn3O4 catalytic + C electrode LIB Anode Area - Discharge e - Wang and Zhou, Journal of Power Sources, 195, (2010), 358 The structure of New Type Lithium Air Battery 33 At high pH condition, the low cost catalysts such as metal oxides can be used. However, at acidic condition, expensive catalyst such as Pt has to be used to reduce O. Now, the LISICION is also weak in strong acidic condition. Advantages at high pH codition： Charge：Air electrode: 4OH- → O2 + 2H2O + 4eAnode: Li+ + e- → Li Discharge：Air electrode: O2 + 2H2O + 4e- → 4OHAnode: Li → Li+ + e- 34 0 1 2 3 4 5 6 10000 OCV 100 -1 20000 200 Capacity ( mAh g ) 0 0 30000 300 Discharge time (hours) 40000 400 60000 Wang and Zhou, Journal of Power Sources, 195, (2010), 358 50000 500 Continue discharge curve Current density is 0.5mA/cm2 Based on the mass of porous catalytic electrode (carbon + binder + catalyst MnOx) Cell Voltage ( V ) 35 Data is not given Data is not given Data is not given Data is not given 730 mAh g-1 50000 mAh g-1 5630 mAh g-1 2825 mAh g-1 1100 mAh g-1 3000 mAh g-1 78000 mAh g-1 Data is not given catalyst) Based on the mass of (carbon + binder + 2000 mAh g-1 1600 mAh g-1 Based on the mass of only carbon P.G.Bruce 2008，ACIE P.G.Bruce 2006，JACS J.Read 2003，JES Toshiba 2005，JPS J.Read 2002，JES K.M.Abrah am 1996，JES Referenc es 0.5 mAcm-1 (100mAg -1) 70mA g-1 50 mA g-1 0.05 mA cm-2 0.01 mA cm-2 0.05 mA cm-2 0.1 mA cm-2 Current density Conventional lithium air battery’s results Comparing with reported capacity of Conventional lithium air battery 36 Li + OH - OH - Li + + LISICON 空気 Air Air Electrode (carbon porous) + Organic electrolyteaqueous Catalyst Anode 金属 Li - Discharge e - Li+ + Li+ OH - O2 + Charge Another cathode electrode ~V 金属Li 金属Li - e- The carbon used in air electrode will be oxidized in charge process to give high charge potential and poor cycle performance. Set up another cathode electrode： (which is only used in charge process) 37 Cell Voltage (V,vs. Li/Li ) 0 1 2 3 4 5 6 0 20 40 50 Time (hours) 30 60 70 Current density is 0.5mA/cm2 Based on the mass of porous catalytic electrode (carbon + binder + catalyst) 10 80 Charge-discharge curves at aqueous electrolyte Li︱organic electrolyte︱LISICON｜KOH Gel｜Mn3O4 catalytic + C electrode + 38 -Z'' (Ohm) 0 110 5 10 15 20 25 30 140 Z' (Ohm) 130 63 Hz 150 0.2Hz 160 Li + OH - OH - Li + + LISICON 空気 Air Air Electrode (carbon porous) + Organic electrolyteaqueous Catalyst Anode 金属 Li - Wang and Zhou, Journal of Power Sources, 195, (2010), 358 The problem of Now’s Lithium Air Battery Lithium ion conductivity of LISICON is poor （1×10-4S/cm at 25oC） ! 120 10000 Hz 0.01Hz Discharge e - The problem of Now’s Lithium Air Battery 39 The another direction is to develop Lithium Fuel Cell based on Now’s concept. The low inherent solubility of Lithium hydroxide Drawback of our developed Li-air batteries 40 + (1) safe of H2’s storage (2)expensive Pt catalyst Now’s problem of H2-Air fuel cell 41 Wang and Zhou, Journal of Power Sources, 195, (2010), 358 Li-Air Fuel Cell H2-Air Fuel Cell New Concept of Li-Air fuel cell 42 LiLi 金属 OH - Li+ LiOHの回収 of LiOH Collection Li+ OH - e- Air 空気 Wang and Zhou, Journal of Power Sources, 195, (2010), 358 It requires cooperation works between the researchers in rechargeable lithium battery and Fuel Cell fields Reproduce LiOHから Liの再生 金属 Metal Li e- The concept for Li Fuel Cell 43 Li + OH - OH - Li + + （１）Rechargeable Li-Air Battery （２）Li-Air Fuel Cell (Lithium Fuel Cell) LISICON 空気 Air Air Electrode (carbon porous) + Organic electrolyteaqueous Catalyst Anode 金属 Li - Discharge e - The directions of the new type Lithium Air Battery 44 • • • • There are still some problems have to solve. Thank Dr. Y. Wang, Dr. H. Li and AIST, JSPS funds. Thank Ohara company providing LISICON films. Thank all of you for your attentions • Developed hybrid electrolytes （Organic／LISICON／aqueous electrolyte） • Developed Li-Cu rechargeable battery. • Developed New Type Li-Air battery. • Developed concept for Li-Air Fuel Cell. Conclusion 45